Modified antioxygenic starch and method of making and using the same



Patented Apr. 23, 1940 UNITED STATES PATENT OFFICE,

Momrmn amoxrcmo s'raacn AND METHOD or MAKING AND usnsc rm:

SAME

Sidney Masher, New York, n. 1., assignor to Musher Foundation Incorporated, New York, N. Y., a corporation of New York N0. mil ing.

Application August 23, 193i), SerialNo. 291,516

7 (Balms. ((1. 99-150) The present invention relates to the preparation of a new antioxygenic material having starch as a base and possessing marked stabilizing and antioxygenic properties particularly 5 when utilized for retarding oxidative deterioration of food and industrial products.

It is a purpose of the present invention to provide new modified starches possessing marked stabilizing and antioxygenic properties which may be widely used to overcome oxldative de 19 Still further objects and advantages will appear from the more detailed description set forth below, it being understood, however, that this more detailed description is given by way of illustration and explanation only, and not by way of limitation, since various changes therein may H be made by those skilled in th; art without departing from the scope and spirit of the present invention.

In accordance with this invention, there may be used any of the starches although particularly corn or tapioca starch is employed. Other starches that areincluded and which may be used for modification in accordance with this inventionare cassava, chestnut, arrowroot,

potato, rye, wheat, oat, rice and sago. The acidi fled, thin-boiling and enzyme modified starches as used particularly inth'e paper-and textile industries are also included.

In accomplishing the above objects, the starch in powdered or concentrated form'is prepared with a minor amount of the water soluble and less preferably the alcohol soluble extracts of unbleached, finely divided, dry milled cereals and grains, which include principally oats, barley and yellow or white maize or 'hominy, 'and also less preferably include rye, rice, wheat, buckwheat and tapioca. v

The cereals may where desired be decorticated or degerininated before extraction. These cere- .als should not be sprouted, fermented, malted or boiled, nor should their starch, protein or gluten be substantially converted, solubilized, gelatinized, or-dextrinized.

and preferably in unbleached condition and dry milled and finely divided, give the highest yield of stabilizing activity in comparison with the otherv cereals when utilized with powdered starch.

The cereal may be dehulled and/or degermi- -nated but for normal commercial manufacture,

the hulls and/or germs may be allowed to remain as part of the cereal. The raw and unbleached by-products from the normal milling of these cereals are also included for extraction purposes. 1

The cereal such as finely divided whole oats should be mixed or agitated thoroughly with a quantity of water for 10 seconds to 1 hour. The

water used should be substantially free of minerals and desirably free of iron and copper.

Any quantity of water may beused to produce a free flowing mixture. For example, 1 part of oats may be mixed with 9 parts of water by, weight. Other proportions may also be used such as from 5'to parts of water to every 1 part of oats. The cat flour suspension should then be subjected to thorough agitation, preferably for a period of about minutes to 1 hour.

It is particularly desirable for the water used 26 .for the extraction to be acidified to a pH of between 5.0and 6.7 before the extraction. A'pH of'6.0 is preferable and this adjustment will result in reduced tendency to fermentation during extraction, higher yields bf extracted materials,

cleaner separation of water soluble and insoluble materials and higher stabilizing value of the exv tract. Y

It is desirable for the temperature of the water at,the time of extraction to be about 135 F. al-

though room temperature is also satisfactory.

After a 30 minute agitation period the solution a should desirably be cooled by. placing it in a jacketed or coiled vat or by water through cooling coils immersed therein so that '50 the temperature of the water isreduced to from 70 Fjto F.

It is not desirable for the extraction to be conducted at above F. because of possibility of gelatinization or conversion of the starch present 45 in the cereal.

dues. This may be accomplished by allowing the mixture to settle for 2 to 12 hours or more until '50 a clear supernatant liquor is formed which liquor is removed by decanting, siphoning or similar process.

The solution may also be subjected to a con- The cereals and particularly the oat, maize and tinuous centrifuging operation whereby un- I barley cereals, and desirably their meal portions,

dissolved material is removed as a continuous operation and a clarified liquor is obtained.

The clear solution thus obtained should desirably be evaporated under reduced pressure at not over about 135 F. and preferably under 25 inches of vacuum, to approximately 25% to 75% total solids and desirably to about 70% total solids and to a Baum of, 37.

The evaporating temperature may vary, dependent upon whether vacuum or atmospheric pressure is used. Although it is desirable to use vacuum evaporation, evaporation at atmospheric pressure may also be employed.

The oat extract thus obtained will be of dark brown or tan color, comparatively solid at 75 F. and liquid at 110 F. to 125 F., flowing freely at that temperature, dependent upon the concentration of solids.

Extracts of other cereals will vary in color and consistency following extraction. The extract of maize or hominy is much lighter in color,

varying from light yellow to light brown, and blander in flavor and odor, and is more desirable for commercial extraction.

Oats and maize will give an extract of substantially greater potency than the other cereals and the yield obtained will also be greater. In the case of oats, it is preferable to use finely divided whole oats with its full content of oat groa-ts and hulls rather than oat flour. There may also less desirably be utilized the cereal middlings and hulls or other residuary products obtained during the milling of the oats.

The extract thus prepared in concentrated form such as, for example, the concentrated water extract of unbleached yellow or white maize or hominy flour may be added to the starch preferably by combining the extract with a concen trated starch solution having 30% or more and desirably about 75% total starch.

, For example, a combination may be made comprising the concentrated water extract of maize flour having 70% total solids with a concentrated starch solution having 65% total starch, and after thorough admixture of the concentrate in the starch solution, the solution containing the concentrate may then be subjected to a further drying operation.

Thecombination may be dried by placing on trays in heated chambers, by spraying into a heated chamber or by running over hot rollers to obtain adrum dried antioxygenic starch.

The combination may where desired by sterilized at temperatures of between 220 F. and 245 F.

It is particularly desirable for the extract to be added to the starch in condensed or concentrated and undrie' form rather than to apply the extract to alrea y powdered starch and then to dry themixture.

The extract must be thoroughly admixed with.

and absorbed upon the individual particles of finished powdered starch in order for the desired reaction to take place whereby the antioxygenic modified powdered starch is obtained.

The amount of the cereal extract to be used on the starch will vary within fairly wide limits such as, for example, from about 0.02% of the cereal extract and 99.98% of the starch on its solids weight basis up to about of the cereal extract and.50% of the starch.

A minor amount of the cereal extract is preferred against the weight of the starch and pref erably less than 5% of the cereal extract is used and 95% or more of the starch on its solids weight basis. For example, it has been found that a particularly desirable combination can be madeby using from 95% to 99.5% by weight of the starch on its solids basis with from 5% to 0.5%

by weight of the cereal extract on its solids 5 weight basis.

starches prepared in this manner will be markedly antioxygenic in character as compared with ordinary starch and even as compared with the cereal extracts themselves. possesses no antioxygenic properties whereas when utilizing the extract-starch combination, I

there is obtained a marked enhancement in stabilizing activity.

Ordinary starch 10 The starch containing the cereal extract may 15 be used in pure oils and fats such as with the essential oils, glyceride oils or hydrocarbon oils and it is extremely elfective when used in aqueous compositions and particularly food compositions which may contain oil globules in the dis- 0 continuous phase thereof or through. Y

The presence of the cereal extract-starch comdispersed theretion to the. discontinuous fat or oil phase although .when added direct. to the fat or oil phase it is comparatively much less efiective.

The cereal extract-starch combination may be bination in the aqueous continuous phase of a food composition gives extremely marked protec- 25 very desirably utilized in the dairy industry, such 30 as for addition to milk, cream, ice cream, cream cheese, condensed and evaporated milk, sherbets, cream in the manufacture of butter, milk for powdering, ,etc., where it serves to retard materially the development of tallowy, oxidized and 35 rancid flavors,

The starch cereal extract combination may also desirably be employed in the manufacture of sausage and particularly fatty sausages which are so subject to oxidative deterioration and rana cidity.

The starch-cereal extract combination is highly desirable for replacement in whole and, less preferably, in part for starch normally employed in the baking industry, as in the manufacture of 45 icings, desserts, cakes, etc., where oxidizable essential oils or glyceride oils are present and which may substantially be protected against oxidative deterioration.

The modified antioxygenic starch may also de- 5 sirably be utilized for sizing purposes as in the sizing of papers, textiles, etc., Where sulfonated and other oxidizable oils are normally used and where the modified starch, applied to the paper or textile as a sizing and in the same manner as ordinary starch is normally applied, will reduce and in many cases prevent the occurrence of oxidized or :rfancid objectionable odors.

Where the starch-cereal extract combination is used in partial or complete replacement for starch normally employed in food compositions subject to oxidation and for industrial purposes, then smaller proportions of the cereal extract may be employed, down to about 0.5% to 2% of the cereal extract against the weight of the 05 starch,

bleached cereals, and for combination with in from 3 to 10 times its" weight of alcohol or similar solvent and agi ting vigorously while holding preferably at a slig tly elevated temperature, as at 100 F. The alcohol may desirably be acidified to a pH of between 5.0 and 6.7 as

when water is used for the solvent.

The alcohol soluble portion is then removed by filtration, siphoning, etc., and the alcohol removed preferably under. reduced pressure and at a low temperature as at about 135 F. Such alcohol soluble extracts are combined with starch in the foregoing manner.

Among the cereals there are also included for water and alcoholic extraction and for combination of such extracts with starch, the cereal germs and other cereal by products, such as corn germ, wheat germ, rice germ, rice polish, etc. These materials are preferably utilized in finely divided, unbleached condition and may, where desired, be deoiled or defatted by expressing or so extracting the fixed glyceride oil therefrom after which they are finely divided and subjected to water or alcoholic extraction and absorbed upon m the starch particles. I

Although the cereals are particularly desired 5 for extraction in accordance with this invention, the unbleached seeds, nuts and fruits, referred to herein as seeds, and particularly the finely divided unbleached seeds, nuts and fruits, such as, for example, sesame, cottonseed, peanuts, 40 soya, sunflower, olives, watermelon seed, etc.,

which have desirably first been substantially deoiled or defatted'by expression or extraction (as with hexane or gasoline) of the fixed 'glyceride oils contained therein maybe utilized for combination with and absorption upon starch in order to produce antioxygenic materials particularly valuable for use in retarding oxidative deterioration of food compositions.

It is important that when the antioxygens are extracted from the cereals or other materials by water or by alcohol, that the antioxygenic substance be in substantially-the same chemical condition as in the original materials when extracted. Moreover, the temperature, acidity and components .of the extracting liquor should not be such as to cause substantial change or breakdown in the antioxygenic complexes which are removed. Boiling, fermentation, malting, sprouting, peptinizingfcausticizing, dextrinizing, etc., are desirably avoided in the extraction procedures' The extract itself contains usually both low an high molecular weight water soluble carbohydrates and also organic nitrogen and phosphorus compounds, all of which are present in complex combination and appear to be essential to obtain the desired action. This modified starch preparation shows particularly marked antioxygenic and stabilizing activity when subjected to elevated temperatures in the presence of oxidizable compositions. For example, where the modified starch containin the cereal extract is heated to in excess of 1&5 F. and preferably above 250 P. in the presence of oximtwmamarkcdem hancement in antioxygenic and stabilizing activity is obtained. x

A heat treatment of as high as 400 F. to 500' a P. will give still further stabilizing action or as little as 1'10 F. will improve the antioxidant ac s tivity of the modified starch. Among other food compositions that may be rendered much more stable to oxidative deteri ration by adding thereto the combination of" starch with the water or alcohol soluble extracts 10 of the cereals, cereal germs or seeds, there are included candles and confections such as tomes, caramelanougats, milk chocolate, buttercreams,

etc., canned foods such as canned soups, creamed soups, milk soups, etc., milk and dairy emulsions, 16 etc.

This application is a continuation in part of application, Serial No. 229,296, filed September 10, 1938, which has matured into Patent No. 2,176,028, and application, Serial No. 249,990 filed 99 January 9, 1939, which has matured into Patent No. 2,176,027.

Having described my invention, what I claim is:

1. A process of stabilizing a glyceride oil con- 25 taining food composition subject to oxidative d6? terioration which comprises extracting an unbleached cereal with slightly acidified water, concentrating said extract, combining said extract with starch, and adding a relatively small pro- 30 portion of said concentrated combination to the food composition, whereby the food composition is stabilized against oxidative deterioration.

2. A process of stabilizing a food composition subject to oxidative deterioration which com- 35 prises extracting unbleached maize with slightly acidified water, combining said extract with starch and adding a relatively small proportion of said combination to the food composition,

whereby the food composition' is stabilized 4nv against oxidative deterioration.

3. A process of stabilizing an organic composition subject to oxidative. deterioration which comprises extracting an unbleached material selected from the group consisting of the cereals, 5

cereal germs andseeds with a solvent selected from the group' consisting of water and alcohol. combining said extract with starch, and adding a relatively small proportion of said combination to the organic composition, whereby the organic 50 composition is stabilized against oxidative deterioration.

4. A stabilized glyceride oil containing foo composition, which is resistant to oxidative deterioration, treatedwith arelatively small pro- 5 portion of a dried combination ofstarch and a slightly acidified water extract of an unbleached cereal.

5. A stabilized organic composition, which is resistant to oxidative deterioration, treated with-. a relatively small proportion of a combination V of starch and an extract of an unbleached material selected from the group consisting of the cereals, cereal germs and seeds, said extract being selected from the group consisting of the 55 water and alcohol soluble extracts.

6. The process of making a dried combination of starch and cereal antioxygens, suitable for addition in small quantities to organic compositions 'subject to oxidative deterioration to stabilize 70 of water and alcohol, and combining said extract with starch.

7. A dried combination of starch and concentrated antioxygens, suitable for addition in small 5 quantities to organic compositions subject to oxidative deterioration to stabilize such compositions against such deterioration, said concentrated antioxygens consisting of the vacuum concentrated antioxy'gens extracted from an unbleached material selected from the group consisting of the cereals, cereal germs and seeds and said'extracts consisting of the slightly acidified,

water and alcohol soluble extracts.

SIDNEY MUSHER. 

